EP3898236A2 - Printable film - Google Patents
Printable filmInfo
- Publication number
- EP3898236A2 EP3898236A2 EP19836432.5A EP19836432A EP3898236A2 EP 3898236 A2 EP3898236 A2 EP 3898236A2 EP 19836432 A EP19836432 A EP 19836432A EP 3898236 A2 EP3898236 A2 EP 3898236A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- silica
- fdm
- film
- multilayer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010410 layer Substances 0.000 claims abstract description 242
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 233
- 239000000203 mixture Substances 0.000 claims abstract description 87
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 86
- 239000003463 adsorbent Substances 0.000 claims abstract description 74
- 239000000741 silica gel Substances 0.000 claims abstract description 59
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 59
- 229920000098 polyolefin Polymers 0.000 claims abstract description 43
- 229920001155 polypropylene Polymers 0.000 claims description 69
- -1 polyethylene Polymers 0.000 claims description 54
- 239000004743 Polypropylene Substances 0.000 claims description 51
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 34
- 239000011148 porous material Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000012792 core layer Substances 0.000 claims description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 26
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 24
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920001038 ethylene copolymer Polymers 0.000 claims description 12
- 229920001897 terpolymer Polymers 0.000 claims description 12
- 230000002087 whitening effect Effects 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 239000007844 bleaching agent Substances 0.000 claims description 7
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 6
- 239000004700 high-density polyethylene Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012748 slip agent Substances 0.000 claims description 5
- 239000012963 UV stabilizer Substances 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 12
- 238000001035 drying Methods 0.000 abstract description 6
- 239000000049 pigment Substances 0.000 abstract description 6
- 239000002356 single layer Substances 0.000 abstract description 4
- 229960001866 silicon dioxide Drugs 0.000 description 57
- 238000000576 coating method Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- 238000003892 spreading Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 239000008188 pellet Substances 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000011800 void material Substances 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920008712 Copo Polymers 0.000 description 5
- 238000009459 flexible packaging Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920003299 Eltex® Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010866 blackwater Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
- B32B27/205—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents the fillers creating voids or cavities, e.g. by stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
-
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Definitions
- the present invention pertains generally to a printable film and more specifically to either a single layer film or a multilayer film usable as synthetic paper having a printable surface for receiving printed indicia from a variety of printing methods, e.g., inkjet, flexographic and gravure.
- the particular printing method employed does not constitute a limitation on the broadest aspects of this invention.
- the synthetic paper of this invention can be converted into labels and similar articles commonly formed from conventional paper substrates.
- paper substrates are required to carry printed indicia applied by inkjet and similar print technology.
- the printed indicia need to be clear, without smudging or similar defects in order to be commercially acceptable.
- WO 2017105404 discloses that an image receiving layer (that does not actually contact the image) needs to be coated with an abrasion resistant layer (that actually contacts the image) consisting of water soluble or water dispersible cross-linked urethane or epoxy binder with filler.
- US 2008075869 A1 discloses a water/solvent based coating process in which the coating has a very low viscosity of less than 1000 centipoise before it is applied and dried.
- the active component in the coating is a fumed or colloidal form of metal oxide.
- US5332548 mentions coating or impregnating a water/solvent-based material by spraying, dipping, brushing, spreading, printing and then drying.
- US7015270 discloses a water-based coating formulation patent.
- the active component in the coating is a fumed metal oxide.
- Silica gel is one of many pigments identified in the patent, which optionally can be included, if desired.
- US 6783816 discloses inkjet coating including a water soluble binder.
- US 7572854 discloses water soluble binders in coatings that are applied to a substrate and dried.
- WO/98 49003 discloses the use of low levels of silica gel as a slip agent or anti-blocking agent.
- the addition level is commonly much lower than 1% and typically measured in parts per million. This is an inadequate level to provide a desired print surface for synthetic paper.
- EP 191 970 5 discloses the use of silica gel in a UV coating to impart roughness. This is known to impart desired anti-blocking behavior or improved slip characteristics; having no bearing on providing a desired print surface for synthetic paper.
- U.S. Patent Nos. 4,892,779; 4,861,644 and 4833172 each disclose an extrusion process employing a technique called thermally induced phase separation used to process ultra-high molecular weight polyethylene where the polymer and fdler are co-extruded with an oil or lubricant sufficient to facilitate extrusion of a cast film where the lubricant or oil is extracted and removed in subsequent processing.
- silica gel included in melt processed films
- prior art generally discloses the use of silica forms (precipitated, colloidal, and gel) and other minerals in very low quantities as anti-blocking agents or slip modifiers. These levels do not provide the desired surface characteristics to enhance print quality; in particular inkjet print quality.
- a pre-compounded, solid blend of a polyolefin and adsorbent silica (not a water or solvent based coating) is employed in an extrusion process to extrude a desired top print layer on a base substrate to form a multilayer structure; most preferably with the top layer and base layer being coextruded.
- the blend of polyolefin and adsorbent silica can be extruded onto the base substrate in an extrusion coating process.
- such extrusion coating can be done i.e. between the machine direction and transverse direction stretching operations in the formation of the film.
- None of the embodiments of this invention requires the use of oils or lubricants to process the polymer matrix, generate pores or for any other purpose. Thus, no such substances need to be extracted subsequently, nor impair the access to the inner surface of such pores if not extracted completely.
- a preferred extruded multilayer film of this invention including a top layer comprising a blend of a polyolefin and adsorbent silica, said silica being at least 5% by weight of the blend, said multilayer film being oriented in at least one direction causing fracturing of said top layer to provide a microporous surface exposing the silica, said fractured top layer being receptive to receive a printing ink on an exposed surface thereof with enhanced pigment entrapment and rapid ink drying.
- the adsorbent silica is present in the range of 5%-30%; more preferably in the range of 10%-25% by weight of the blend in the top layer and even more preferably in the range of 15%-20% by weight of the blend in the top layer.
- acceptable print quality can be obtained either with or without prior oxidative treatment (e.g., corona, flame or plasma treatment) of the printable layer.
- oxidative treatment e.g., corona, flame or plasma treatment
- the adsorbent silica employed in the blend includes pores having a diameter greater than 30 angstroms, preferably greater than 60 angstroms, and more preferably greater than 100 angstroms and most preferably in the range of 100 to 300 angstroms. While the pore size should be large to avoid capillary condensation of water at common environmental conditions, the surface area should also be high to facilitate high adsorption capacity.
- a method to determine the internal surface area of the adsorbent silica is commonly known as BET adsorption isotherm and is determined by ASTM D 1993 -03.
- Suitable adsorbent silicas provide an internal pore surface area as per BET adsorption isotherm of greater than 10 m 2 /g, more preferably greater than 20 and even preferably greater than 50m 2 /g. Higher internal pore surface areas of greater than 100 m 2 /g but less than 700 m 2 /g are even more desirable, preferably between 200 and 700 m 2 /g, and most preferably between 200 and 400 m 2 /g.
- the polyolefin in the polyolefin/adsorbent silica blend includes one or more polyolefins from the group consisting of polypropylene homopolymer, polyethylene including high density polyethylene, propylene/ethylene copolymers,
- a co-extruded, multilayer fdm includes a core layer, a top layer on one side of the core layer and including the blend of polyolefm/adsorbent silica therein and a bottom layer on the opposed side of the core layer, said bottom layer preferably being a bonding layer for permitting bonding of the multilayer fdm to another article.
- the top layer including the blend of polyolefm/adsorbent silica therein also includes a void creating agent (e.g., calcium carbonate, polybutylene terephthalate), a whitening agent (e.g., titanium oxide), or a combination of both a void creating agent and whitening agent therein.
- a colorant or pigment can be included in the top layer or any of the other layers to provide a desired color to that layer or layers.
- the preferred multilayer fdms of this invention are polypropylene fdms, i.e., each layer including greater than 50% polypropylene therein.
- “propylene polymer,” unless indicated otherwise, means a propylene homopolymer (“Homo PP”), or a copolymer (“Copo”) or a terpolymer (“Terpo”) in which the predominant monomer component, by weight, is propylene.
- Homo PP propylene homopolymer
- Copo copolymer
- Terpo terpolymer
- references to“propylene terpolymer,” unless indicated otherwise, means a terpolymer comprising propylene (“C3”), ethylene (“C2”), and butene-1 (“C4”) monomer units in which propylene is the predominant monomer unit by weight.
- references to“propylene copolymer,” unless indicated otherwise, means a copolymer comprising propylene (“C3”), and ethylene (“C2”), or butene-1 (“C4”) monomer units in which propylene is the predominant monomer unit by weight.
- Reference to“propylene homopolymer,” unless indicated otherwise means a homopolymer and also a propylene -ethylene copolymer in which the percentage of ethylene is so little that it doesn’t adversely affect the crystallinity or other properties of the homopolymer. These copolymers are referred to as“mini-random” copolymers and have a percentage ethylene, by weight of the copolymer, of 0.8% or less.
- organic and inorganic materials usable in this invention are:
- the adsorbent silica and other additives can be combined in high concentrations with one or more polymers to form a masterbatch.
- the masterbatch may be used directly or mixed as a solid or melt with other polymers, additives, or masterbatches to form a blend that can be coextruded, extruded, or extrusion coated.
- the masterbatch can include one or more additives from the group consisting of antistatic agents, slip agents, whitening agents, voiding agents, UV stabilizers, UV absorbers, antioxidants, and acid scavengers.
- Figs 2A and 2B include photographs of 10 commercial synthetic papers.
- An extruded multilayer fdm of this invention includes an extruded top layer comprising a blend of one or more polyolefins and adsorbent silica, said adsorbent silica being present in at least 5% by weight of the blend; over 50% of the blend, by weight, being the polyolefins.
- the multilayer film is oriented in at least one direction causing fracturing of said top layer to provide a microporous surface exposing the adsorbent silica, said fractured top layer being receptive to receive a printing ink on an exposed surface thereof with enhanced entrapment of the colorant in the ink and rapid ink drying.
- the printing ink can be applied in discontinuous or continuous coating. Other coatings could also be applied and benefit from enhanced entrapment of colorant in the ink, more rapid coating drying, and/or better coating adhesion.
- the adsorbent silica is a silica gel.
- the adsorbent silica can be a precipitated silica.
- adsorbent silica embedded in a polyolefin surface as described above.
- the blends of this invention when melted and extruded to form the top layer of the film provide improved printability relative to water or solvent based blends employed as a coating to form a top surface.
- a benefit of the preferred coextruded embodiments of this invention is that the top layer intimately bonds with the base layer as a result of the co-extrusion of the melts, thereby minimizing the likelihood of undesired flaking of the top, printable layer from the base layer. Such flaking is likely to occur in prior art structures employing water or solvent based coatings.
- olefin binders of this invention are not sensitive to water or solvent exposure, so printing of the top surface is more durable than films with other types of top layers.
- the olefin binder blends of this invention are not brittle, and also provide a strong bond to the supporting base layer so the print skin is unlikely to crack.
- the co-extrusion of the olefm/silica gel skin layer with a base layer in accordance with the most preferred embodiment of this invention is more cost effective than applying water or solvent based coating of the silica gel as a top layer.
- the silica must be an adsorbent silica not, a fumed, colloidal, calcined, fused, pyrogenic, or crystalline silica, nor any other type of silica with little adsorbent properties.
- Adsorbent silica - unlike other forms of silica, has a desired internal porosity to help adsorb the printing ink solvents employed in an inkjet printing or similar operation. It also is important that the pore size be large enough so that moisture adsorption of water from ambient surroundings does not adversely affect the extrusion operation or the print quality of the print-receiving layer.
- the adsorbent silica employed in the blends is a silica gel including pores having a size (diameter) greater than 30 angstroms, preferably greater than 60 angstroms, more preferably greater than 100 angstroms and most preferably in the range of 100 to 300 angstroms therein.
- Preferred size of the silica gel particles is 0.5 to 5 microns.
- adsorbent silica of a large internal pore surface area To ensure rapid drying it is desirable to use adsorbent silica of a large internal pore surface area.
- the internal surface area exceeds 700 m2/g the pore size becomes so small that the adsorbent silica becomes capable of condensing water from common humid environmental air conditions. This results in fdling the pores with water and leaving reduced capacity to adsorb liquids associated with the ink.
- This critical level of internal pore surface area is commonly observed when the pore size is less than 30 angstroms.
- a method to determine the internal surface area of the adsorbent silica is commonly known as BET adsorption isotherm.
- Suitable adsorbent silicas provide an internal pore surface area as per BET adsorption isotherm of greater than 10 m 2 /g, more preferably greater than 20 and even preferably greater than 50 m 2 /g. Higher internal pore surface areas of greater than 100 m 2 /g but less than 700 m 2 /g are even more desirable, preferably between 200 and 700 m 2 /g, and most preferably between 200 and 400 m 2 /g.
- Adsorbent silica expected to meet these criteria would be those produced through a gel or precipitation process, commonly referred to as silica gel or precipitated silica, respectively.
- An empirical correlation between pore volume and pore diameter is known to those skilled in the art. For example, in a Fuji Silysia Chemical, Ltd. publication a table is presented stating that a pore volume of 1.8, 1.6, 1.25, 0.8, and 0.44 ml/g of adsorbent silica corresponds to a pore diameter of 240, 210, 170, 70, and 25 Angstrom, respectively.
- adsorbent silica grades including pores of a diameter greater than 30 angstrom, preferably greater than 60 angstroms, and more preferably greater than 100 angstroms and most preferably from 100 to 300 angstroms.
- the physical properties of the adsorbent silica can be altered by changing production conditions.
- the pore size desirable for employing silica as an anti-block agent or a slip agent is extremely small; well outside the desired range for achieving accepted, commercial print quality, as applicant has discovered in this invention.
- acceptable print quality can be obtained either with or without oxidative treatment of the top, printable layer; depending on the dyne level of that layer.
- “Dyne level” is the surface tension of a solvent that is able to wet the surface of the open-porous top layer through interacting either with the polar surface of the adsorbent silica; most preferably silica-gel particles, or with polar groups on the surface of the top layer, when the top layer is oxidatively treated.
- the test method for determining the dyne value is ASTM D2578-09. Specifically, it is desirable to achieve a dyne level, tested after 1 week of aging or more, greater than 35, preferably greater than 38, more preferably 41.
- a dyne level of 44 and most preferably greater than 50 is desirable.
- the dyne value can be increased by increasing the amount of adsorbent silica in the blend and also by oxidatively treating the top layer; most preferably by corona treatment. If the amount of adsorbent silica in the blend provides a dyne value in excess of 50 it may not be necessary to also oxidatively treat the print surface.
- the surface can be oxidatively treated to provide the desired dyne value to achieve acceptable print quality.
- the polyolefin employed in the blend of polyolefin and adsorbent silica of this invention is one or more of the polyolefins from the group consisting of polypropylene homopolymer, polyethylene including high density polyethylene, propylene/ethylene copolymers, maleated polypropylene, and incompatible blends of a polypropylene with a polyethylene or another poly alpha-olefin or incompatible blends of polyethylene with another poly alpha-olefin and propylene/ethylene/butene -1 terpolymers and combinations thereof.
- the bonding layer can be a cold seal layer, a heat seal layer or a pressure sensitive layer.
- Such layers are disclosed in numerous patents, and are well known to those skilled in the art.
- heat sealing resins can include Eltex P KS409 from Ineos, a C2C3 copolymer having a melting point of 134 C, DS6D82 from Braskem, a C2C3 copolymer having a melting point of 133C, Eltex P KS 359 from Ineos, a C2C3C4 terpolymer having a melting point of 134C, and Adsyl 5C39F from LyondellBasell, a C2C3C4 terpolymer having a melting point of 134C.
- Exemplary cold seal adhesives are Turbo-seal C1775B manufactured by Bostik and Loctite Liofol CS22-861US1 manufactured by Henkel.
- Examples of pressure sensitive adhesives include Aroset 2529 from Ashland Chemical or Covinax 300-01 from Franklin Adhesives and Polymers. These are only exemplary of the numerous cold seal and pressure sensitive adhesives that can be used in this invention.
- a co-extruded, multilayer film comprises at least three layers including a core or base layer, a top layer including the blend of polyolefm/adsorbent silica on one side of the core or base, layer, a bottom layer on the opposed side of the core or base layer, said bottom layer comprising a blend of non-compatible polymers, i.e. a polyethylene and a polypropylene, with a rough surface morphology, said bottom layer being a bonding layer for facilitating bonding or attachment to an injection molded, blow-molded, or thermoformed article in an in-mold label (IML) process.
- IML in-mold label
- the multilayer film can be converted into IML product labels for attachment to packaging for the product through the bottom bonding layer.
- a co-extruded, multilayer film comprises at least four layers including a core or base layer, a top layer including the blend of polyolefin/ adsorbent silica on one side of the core or base, layer, a bottom layer on the opposed side of the core or base layer, and a tie layer between the core layer and the bottom layer.
- the tie layer between the core layer and the bottom layer comprising a maleated polypropylene, said bottom layer comprising one or more polyamides preferably used as being a bonding layer for facilitating bonding of the multilayer film to another article.
- the multilayer film of such embodiment can be converted into pressure sensitive product labels for attachment to packaging for the product through the bottom bonding layer.
- a tie layer can be employed to improve the adhesion of the adsorbent silica-containing top layer to the core layer, and/or the adhesion of the core layer to the lower bonding layer.
- Tie layer materials that are known improve the adhesion between dissimilar materials and include maleated polypropylene such as Admer QF500A sold by Mitsui.
- Tie layers such as polypropylene between the adsorbent silica-containing layer and a voided core may also be included on either or both sides of voided a core to improve stiffness.
- the top layer including the blend of polyolefm/adsorbent silica therein also can include a void creating agent (e.g., calcium carbonate or poly butylene terephthalate), a whitening agent (e.g., titanium oxide), or a combination of both a void creating agent and whitening agent therein.
- a void creating agent e.g., calcium carbonate or poly butylene terephthalate
- a whitening agent e.g., titanium oxide
- Representative void creating agents and whitening agents are PF97 and P8266 from A. Schulman, respectively, as identified in the earlier presented chart identifying components usable in this invention.
- the void creating agent and polyolefin are added in the form of the identified blend or as separate components. However, when a void creating agent is used, it is preferred to include it in the
- a coextruded three-layer film of paper-like appearance is oriented in at least one; preferably in 2 directions, with an exposed top layer, a base or core layer and an exposed bottom layer on the opposite side of the core layer.
- the film is characterized in that the core layer comprises a voiding agent, preferably polybutylene terephthalate, and optionally a whitening agent, and is thicker than the exposed top or bottom layers.
- the top layer is a polyolefm/adsorbent silica blend.
- the polyolefin includes a blend of a one or more polymers from the group consisting of polypropylene homopolymer, polyethylene including high density polyethylene, propylene/ethylene copolymers, maleated polypropylene, incompatible blends of propylene and ethylene polymers or propylene and another alpha-olefin, incompatible blends of ethylene with another alpha-olefin, and propylene/ethylene/butene- 1 terpolymers and combinations thereof.
- the polyolefin in the top layer is a polypropylene or more preferably a propylene ethylene copolymer.
- Said bottom layer of said coextruded oriented three-layer fdm of paper-like appearance is a bonding layer for permitting bonding of said three-layer fdm itself a through heat sealing or through application of a cold seal adhesive to, e.g., form flexible packaging, or bonding to another article directly or through application of an adhesive.
- said top layer of said coextruded oriented three-layer film of paper-like appearance comprises additionally a whitening agent and optionally a voiding agent.
- the polyolefin includes a blend of a one or more polymers from the group consisting of polypropylene homopolymer, polyethylene including high density polyethylene, propylene/ethylene copolymers, maleated polypropylene, incompatible blends of propylene and ethylene polymers or propylene and another alpha-olefin, incompatible blends of ethylene with another alpha-olefin, and propylene/ethylene/butene- 1 terpolymers and combinations thereof.
- the polyolefin in the top layer is a polypropylene or more preferably a propylene ethylene copolymer.
- the polyolefin in the top layer is present in a weight percentage of 95 to 70%, preferably 90 to 75% and more preferably 85 to 80% by weight, and the adsorbent silica is present in a weight percent of 5 to 30%, preferably 10 to 25% and more preferably 15-20%, respectively.
- the adsorbent silica is a silica gel including pores having a diameter of at least 30 angstroms, preferably greater than 60 angstroms, more preferably greater than 100 angstroms and most preferably in the range of 100 to 300 angstroms therein.
- said top layer of said coextruded oriented five-layer film of paper-like appearance comprises additionally a whitening agent and optionally a voiding agent.
- the bottom tie layer between the core layer and the bottom layer of said coextruded oriented five-layer film of paper-like appearance comprises a polyolefin, preferably a polypropylene, most preferably at least 50% by weight of a polypropylene and optionally a whitening agent and, as another option, additionally a voiding agent.
- the bottom layer of this coextruded five layer film comprises more than 50% by weight of polypropylene, preferably a propylene ethylene copolymer, and constitutes a bonding layer for permitting bonding of said five-layer film through heat sealing or through application of a cold seal adhesive to said bonding layer, e.g., to form flexible packaging, or bonding to another article directly or through application of an adhesive to said bonding layer.
- said bottom tie layer between the core layer and the bottom layer comprises a maleated polypropylene, said bottom layer, comprising one or more polyamides; preferably is used as a bonding layer for facilitating bonding of the multilayer film to another article.
- the multilayer film of such embodiment can be converted into pressure sensitive product labels for attachment to packaging for the product through the bottom bonding layer.
- the lucent layer is not a crystal-clear layer in that it is somewhat foggy or icy, having a general matte appearance. However, the lucent layer is visually transparent; permitting individuals to view through it.
- the layers in addition to the top layer are free of void creating and/or whitening agents.
- the entire multi-layer film is translucent in a way frequently identified as contact transparency; permitting the viewing of text through the film.
- Another preferred embodiment of this invention is a coextruded multi-layer film of translucent appearance oriented in at least one; preferably in 2 directions, with an exposed top layer, a base or core layer and an exposed bottom layer on the opposite side of the core layer, and optionally with tie layers between the core layer and the top layer, and between the core layer and the bottom layer, characterized in that said core layer is thicker than said exposed top or bottom layers.
- the polyolefin in the top layer is present in a weight percentage of 95 to 70%, preferably 90 to 75% and more preferably 85 to 80% by weight, and the adsorbent silica is present in a weight percent of 5 to 30%, preferably 10 to 25% and more preferably 15-20%, respectively.
- the adsorbent silica is a silica gel including pores having a diameter of at least 30 angstroms, preferably greater than 60 angstroms, more preferably greater than 100 angstroms and most preferably in the range of 100 to 300 angstroms therein.
- Each of the core and the optional tie layer comprises more than 50% by weight of polypropylene.
- said exposed top layer may be oxidatively treated, preferably corona treated, in order to increase its wettability.
- the bottom tie layer between the core layer and the bottom layer of said coextruded oriented five-layer film of translucent appearance comprises a polyolefin, preferably a polypropylene, and most preferably at least 50% by weight of a polypropylene.
- the bottom layer of this five- layer structure comprises more than 50% by weight of polypropylene, preferably a propylene ethylene copolymer, and constitutes a bonding layer for permitting bonding of said multi layer film itself a through heat sealing or through application of a cold seal adhesive to said bonding layer, e.g., to form flexible packaging, or bonding to another article directly or through application of an adhesive to said bonding layer.
- said bottom tie layer between the core layer and the bottom layer comprises a maleated polypropylene
- said bottom layer, comprising one or more polyamides is preferably used as being a bonding layer for facilitating bonding of the multilayer film to another article.
- the multilayer film of such embodiment can be converted into pressure sensitive product labels for attachment to packaging for the product through the bottom bonding layer.
- a solid, particulate blend, or masterbatches for use in extruding a film layer, said blend including 95% to 55% polyolefin and 5% to 45% adsorbent silica; more preferably 85% to 70% polyolefin and 15% to 30% adsorbent silica.
- These blends optionally include one or more additives from the group consisting of antistatic agents, slip agents, whitening agents, voiding agents, UV stabilizers, UV absorbers, antioxidants, and acid scavengers.
- These blends are used to extrude as a printable layer of a multilayer film and labels made from such film and are solid prior to being melted in the extruder, and therefore do not include any water or liquid solvent carrier.
- These blends, as far as they are formulated without, and free of whitening or voiding agents, are also used to extrude as a printable layer of a translucent multilayer film and labels made from such film.
- a master batch consisting of 25%, by weight, silica gel (Syloid C 805) from Grace Davison and 75%, by weight, propylene/ethylene copolymer (propylene copolymer comprising 2.5% of ethylene: Ineos R08G-00) was compounded on a vented twin screw extruder (a ZE75R UTX x56D line from Berstorff, equipped with a melt pump, screen changer, diverter valve, and underwater pelletizer) with the copolymer (Copo) conventionally fed through the extruder throat.
- the silica gel was fed using two feeders, both Brabender DDSR60 twin screw powder feeders with 65 mm and 75 mm pitch concave intermeshing screws.
- the material was pelletized using a Gala EAC 6 with a 48 hole die.
- the first pass achieved a 10% silica gel content with 5% from each feeder.
- This 10% compounded material was fed again though the extruder throat in a second pass resulted in a 20% silica gel content again with the addition evenly split between the two feeders.
- the third pass increased the silica gel content to 25% with the addition of 5% silica gel from only one of the feeders.
- the polymer pellets were dried at 70C at -40C dew point.
- the 25% silica gel masterbatch was then blended with pellets of AMPLIFY EA100 (Dow Chemical), an ethylene-ethyl acrylate copolymer.
- the resulting mixture was 21% Silica gel, 16% AMPLIFY, and 63% propylene/ethylene copolymer.
- the blend was co-extruded with a base layer of
- homopolymer polypropylene (H03G06 from Ineos) as a skin layer of a cast sheet.
- the target thickness of the whole cast sheet was 1000 microns, of the skin 200 micron.
- the cast sheet was cooled on a pair of 60C chill roll.
- the cast sheet was heated on a couple of rollers to 135C and stretched 5x in the machine direction between 2 rollers heated to 135C running at different speeds and then pre heated to 175C in the tenter oven and stretched lOx at 153C.
- the biaxially oriented film was then annealed at 162C.
- the 25% silica gel master batch pellets from Example 1 were blended with pellets of maleated PP (Admer QF 500A from Mitsui). The blend resulted in a composition of 12.5% Silica gel, 50% maleated PP, and 37.5% propylene/ethylene copolymer.
- the blend was co extruded with a base layer of homopolymer polypropylene (H03G06 from Ineos) as a skin layer of a cast sheet.
- the target thickness of the whole cast sheet was 1000 microns, of the skin 200 micron.
- the cast sheet was cooled on a pair of 60C chill roll.
- the cast sheet was heated to 135C on a couple of rollers and stretched 5x in the machine direction between 2 rollers heated to 135C running at different speeds and then pre heated 175C and stretched lOx at 153C and then annealed at 162C. Separate samples of this film were formed; one being corona treated on the silica gel skin side and the other being untreated on the silica gel skin side.
- the copolymer resin was fed into the vented twin screw extruder using Brabender single screw FW80/6 Plus.
- the silica gel was fed into the vented twin screw extruder using two Brabender DDSR60 twin screw feeders with 65 mm and 75 mm pitch concave intermeshing screws.
- the material was pelletized using a Gala EAC 6 with a 48 hole die with 0.110” (2.80 mm) diameter holes in a single hole pattern.
- the first pass achieved a 10% silica gel content with 5% from each feeder.
- the polymer pellets were dried at 70C at -40C Dew point.
- the blend was co-extruded with a base layer of homopolymer polypropylene (H03G06 from Ineos) as a skin layer of a cast sheet.
- the target thickness of the whole cast sheet was 1000 microns and of the skin was 200 microns.
- the cast sheet was cooled on a pair of 60C chill roll.
- the cast sheet was heated to 135C on a couple of rollers and stretched 5x in the machine direction between 2 rollers heated to 135C running at different speeds and then pre heated 175C and stretched lOx at 153C and then annealed at 162C. Separate samples of this film were formed; one being corona treated on the silica gel skin side and the other being untreated on the silica gel skin side.
- the 10% silica gel master batch from Example 3 was blended with maleated PP (Admer QF 500A from Mitsui). The blend resulted in a composition of 5% Silica gel, 50% maleated PP, and 45% propylene/ethylene copolymer (R08G-00 from Ineos). The blend was co-extruded as a skin layer on a cast sheet of HomoPP H03G06 (Ineos). The blend was co-extruded with a base layer of homopolymer polypropylene (H03G06 from Ineos) as a skin layer of a cast sheet. The target thickness of the whole cast sheet was 1000 microns, of the skin 200 micron.
- the cast sheet was cooled on a pair of 60C chill roll.
- the cast sheet was heated to 135C on a couple of rollers and stretched 5x in the machine direction between 2 rollers heated to 135C running at different speeds and stretched 5x in the machine direction and then pre heated 175C and stretched lOx at 153C and then annealed at 162C. Separate samples of this fdm were formed; one being corona treated on the silica gel skin side and the other being untreated on the silica gel skin side.
- the film samples were taped to a piece of paper to enable feeding into an HP Officejet 4635 with an HP Ink cartridge 61 (Product# B4L04A).
- An image of 7 colored lines red, purple, blue, green, yellow, orange, red/orange) was printed on each of the samples.
- the ranking from worst performance to best performance was: severe, significant, moderate, slight, and none.
- the office paper control (the sample identified as“Paper”) showed no smearing (none), as can be seen in the photograph.
- a commercial film stock (LIX 60 from applicant) specifically formulated for excellent print performance also was tested. A photograph of this commercial film is shown above and the test results are reported in Table 1 above as well.
- silica gel treated and untreated film surfaces of this invention were the best, with no evidence of smearing after 5 minutes and possessing good initial line image quality, even the 5% silica gel surface delivered improved performance over the LIX60 commercial label film and several of the 10 commercial synthetic papers evaluated, as discussed in greater detail below.
- the inkjet printing performance of the surface improved with increased silica gel content.
- water contact angle commonly is used to characterize the extent of wettability between a surface and a liquid.
- the contact angle is measured by placing a 2 microliter drop of water on the film surface, waiting 25 seconds, and then measuring the angle between the solid surface and liquid. Measurement can be made with a goniometer, such as the DSA 25model sold by Kruss of Hamburg, Germany.
- the average value of water contact angle for the above commercial synthetic papers is only 76 degrees, which is consistent with the general expectation that printability is improved if the water contact angle is less than 90 degrees.
- the ten commercial synthetic papers identified above are polypropylene based films coated with polymer binder and fillers. These commercial synthetic papers also where tested for smearing. Photographs of these ten commercial samples (two sets of 5 photographs) are shown in Figures 2A and 2B. Table 3 below includes a ranking of the smear properties of the ten commercial samples shown in Figure 2A and 2B. Table 3
- this invention provides substantially better print qualities than the identified commercial synthetic papers; particularly with respect to ink smearing. It is difficult to balance the need for ink smear resistance, which is related to adsorption of the ink liquids, against the need to avoid the undesirable lateral spread of ink, which can impair image quality. Generally speaking, it is the current state of the art in commercial synthetic papers that the inclusion of too much adsorbent tends to cause undesired, excess lateral ink spreading.
- the smearing tendency of a print surface is measured by first applying a 0.5 m ⁇ drop of a water based inkjet ink (Cannon Cyan GI-290) to the surface of the film. Then a squeegee that does not absorb the ink is positioned at a steep angle to one side of the drop and then pulled over the drop and along the print surface until all ink is smeared down the film surface.
- the ink fluids are adsorbed and the dye or pigment in the ink delineates the area required to accomplish the adsorption.
- the area of the colored region is then measured. The process is repeated 10 times and the area of the colored region for the 10 samples is averaged.
- a 0.5 m ⁇ drop of black water based inkjet ink (Epson Black 664) is dispensed on to the printable surface with a pipet.
- the drop is permitted to spread for 5 minutes to thereby form a spot.
- the diameter of the spot is measured and the area calculated. This procedure is repeated 5 times and the average ink spot area is calculated.
- the area reflects the spreading behavior. The larger the area, the more spreading has occurred on the film. To promote good image quality it is desirable to minimize ink spreading.
- the printable surface in the films of this invention exhibit the unexpected feature that printability is improved for water-based inkjet ink if the contact angle increases.
- Table 5 shows the water contact angle for examples 1, 3, and 4 described above. The printing images for these examples are shown in photographs above.
- Examples 5-8 are additional, non-limiting examples of films within the scope of this invention and the manner in which such films were made.
- the dynes and water contact angle for these additional 4 examples are shown in Table 6, following the description of these latter examples.
- Example 5 A 25% silica gel master batch was produced by successive passes through a twin-screw compounding extruder.
- 1800 g homo PP (FF030F2 from Braskem) pellets (or compounded pellets) were coated with lOOg of mineral oil (Howard Cutting Board Oil, Howard Products Inc.) and were then blended with up to 10% silica gel (Syloid C 805) particles.
- the mixture was fed into a lab twin screw extruder to produce strands that were water quenched and chopped into pellet. The pellets were dried overnight at 60C.
- 10% silica gel containing pellets were recoated with lOOg mineral oil content and blended again with 10% Silica gel particles and again extruded in the twin screw compounding extruder.
- the pellets were dried over night at 60C.
- the 20% silica gel containing pellets were recoated with lOOg mineral oil and again blended with 5% silica gel particles and extruded in the twin screw compounding extruder, then dried at 60C overnight.
- the 25% silica gel pellets were co-extruded with a base layer of homopolymer polypropylene.
- a cast sheet has been produced with a target thickness of the whole sheet of 1000 microns, of the skin 200 micron (FF030F2 from Braskem) as a skin layer of a cast sheet.
- the fdm was then biaxially oriented simultaneously 5x5 in a T.M. Long Stretcher at 145C.
- a silica gel (Syloid C 805) compound using a pre-compounded PP/PE matrix was produced in a manner described in Example 5 except that the polymer olefin binder in the master batch was a compound of propylene ethylene copolymer / HOPE (MT 0523 DP from Tosaf).
Abstract
Description
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US20040151934A1 (en) | 2003-01-27 | 2004-08-05 | Schwark Dwight W. | Oxygen scavenging film with high slip properties |
EP1721737B1 (en) * | 2004-02-19 | 2016-11-09 | Toyo Seikan Kaisha, Ltd. | Plastic multilayer structure |
US20070036909A1 (en) | 2005-08-09 | 2007-02-15 | Shifang Luo | Processes for producing oriented polymeric films provided with UV-active coatings |
CA2663120A1 (en) | 2006-09-26 | 2008-04-03 | Evonik Degussa Corporation | Multi-functional paper for enhanced printing performance |
EP3341213B1 (en) | 2015-12-15 | 2020-09-30 | Hewlett-Packard Development Company, L.P. | Embossed print media |
JP6832715B2 (en) * | 2017-01-18 | 2021-02-24 | 共同印刷株式会社 | Packaging bag and its manufacturing method |
-
2019
- 2019-12-16 WO PCT/US2019/066564 patent/WO2020131709A2/en active Application Filing
- 2019-12-16 AU AU2019405454A patent/AU2019405454B2/en active Active
- 2019-12-16 BR BR112021011772-5A patent/BR112021011772A2/en not_active Application Discontinuation
- 2019-12-16 US US17/414,769 patent/US11752739B2/en active Active
- 2019-12-16 CA CA3122704A patent/CA3122704A1/en active Pending
- 2019-12-16 EP EP19836432.5A patent/EP3898236A2/en active Pending
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- 2021-06-18 CO CONC2021/0008013A patent/CO2021008013A2/en unknown
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MX2021007367A (en) | 2021-09-23 |
US11752739B2 (en) | 2023-09-12 |
CL2021001582A1 (en) | 2022-01-28 |
US20220063251A1 (en) | 2022-03-03 |
BR112021011772A2 (en) | 2021-08-31 |
AU2019405454A2 (en) | 2021-07-08 |
AU2019405454B2 (en) | 2023-12-14 |
WO2020131709A2 (en) | 2020-06-25 |
CO2021008013A2 (en) | 2021-09-20 |
AU2019405454A1 (en) | 2021-06-24 |
WO2020131709A3 (en) | 2020-10-08 |
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